High-strength moisture-proof gypsum board and preparation method thereof

Abstract

The invention discloses a high-strength moisture-proof gypsum board and a preparation method thereof, and relates to the technical field of gypsum board preparation. The high-strength moisture-proof gypsum board is prepared by dipping the surface paper in the composite dipping liquid and then pouring the surface paper and the gypsum core with the waterproof agent, the composite dipping liquid comprises the methoxy vinyl ether copolymer and the epoxy polyoxymethylene dimethyl ether, and the methoxy vinyl ether copolymer is 2, 3, 5-trimethyl-1, 3-pentanediol monoisobutyrate. According to the present invention, epoxy polyoxymethylene dimethyl ether is prepared by reacting 2, 4-dimethoxymethoxyphenylacetic acid with 2-hydroxyethyl vinyl ether, and the epoxy polyoxymethylene dimethyl ether is prepared by terminating polyoxymethylene dimethyl ether with allyl and then reacting with phthalimide hexperoxy acid, such that the waterproofness and the mechanical property of the gypsum board are improved; the waterproof agent is prepared by reacting hydrogen-containing silicone oil and fluorine-containing hyperbranched amide polyurea urethane, so that the moisture resistance and bonding strength of the gypsum board surface paper are enhanced, and additional mechanical support is provided for the gypsum board.

Description

Technical Field

[0001] This invention relates to the field of gypsum board preparation technology, specifically to a high-strength moisture-proof gypsum board and its preparation method. Background Technology

[0002] Gypsum board is relatively lightweight, has high strength, is thin, easy to process, and offers sound insulation, heat insulation, and fire resistance, making it one of the new lightweight building materials currently under development. At present, gypsum board is widely used in interior partitions, ceilings, sound-absorbing panels, floor baseboards, and various decorative panels in various buildings such as residences, office buildings, shops, hotels, and industrial plants.

[0003] Strength and waterproof / moisture-proof properties are two key concerns for customers regarding the quality of gypsum board. To further improve the strength and moisture-proof stability of gypsum board, this invention researches and prepares a high-strength moisture-proof gypsum board to solve this problem. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a high-strength moisture-proof gypsum board that is made by impregnating the face paper in a composite impregnation liquid and then casting it with a gypsum core containing a waterproofing agent, thus having high strength and moisture-proof performance.

[0005] The present invention proposes a technical solution to solve the above-mentioned technical problems: a high-strength moisture-proof gypsum board, characterized in that it comprises the following raw material components in parts by weight: a face paper is impregnated in a composite impregnation liquid, and then cast with a gypsum core containing a waterproofing agent; the composite impregnation liquid comprises nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer, and epoxy polyoxymethylene dimethyl ether; the gypsum core comprises gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent, retarder, and glass fiber.

[0006] Preferably, the composite impregnation solution comprises a methoxyvinyl ether copolymer and an epoxy polyoxymethylene dimethyl ether; the methoxyvinyl ether copolymer is prepared by reacting 2,4-dimethoxymethoxyphenylacetic acid with 2-hydroxyethyl vinyl ether; the 2,4-dimethoxymethoxyphenylacetic acid is prepared by demethylating 2,4-dimethoxyphenylacetic acid to generate 2,4-dihydroxyphenylacetic acid, reacting it with chloromethyl methyl ether, and finally hydrolyzing it; the epoxy polyoxymethylene dimethyl ether is prepared by first end-capping polyoxymethylene dimethyl ether with allyl groups, and then reacting it with phthalimide peroxyacid.

[0007] Preferably, the waterproofing agent is prepared by reacting hydrogen-containing silicone oil with fluorinated hyperbranched amide polyurethane; the fluorinated hyperbranched amide polyurethane is prepared by reacting dodecafluoroheptyl methacrylate with epoxy polyamide-amine, and then reacting with hyperbranched polyurethane; the epoxy polyamide-amine is prepared by reacting hyperbranched polyamide-amine with epichlorohydrin.

[0008] Preferably, the foaming agent is sodium dodecyl sulfate; the retarder is sodium citrate.

[0009] Preferably, the preparation method of the high-strength moisture-proof gypsum board includes the following specific steps: S1. Mix ethyl 2,4-dihydroxyphenylacetate and dichloromethane at a mass ratio of 1-1.2:15, cool to 2-4°C, add 0.6-0.8 times the mass of ethyl 2,4-dihydroxyphenylacetate in sodium hydride, and add 1.9-2.1 times the mass of ethyl 2,4-dihydroxyphenylacetate in chloromethyl methyl ether at 200-400 rpm. Heat to room temperature and continue stirring for 10-12 hours. After rotary evaporation, extract with dichloromethane and deionized water, separate by column chromatography using petroleum ether and ethyl acetate at a volume ratio of 4:1, and distill under reduced pressure. Add 7-9 times the mass of ethyl 2,4-dihydroxyphenylacetate in anhydrous ethanol and 0.2-0.3 times the mass of ethyl 2,4-dihydroxyphenylacetate in potassium hydroxide, heat to 32-35°C, react for 4-6 hours, cool to room temperature, and add 2,4-dihydroxyphenylacetate dropwise at a rate of 1-3 ml / min. 2,4-Dimethoxymethoxyphenylacetic acid was prepared by vacuum distillation of 2.1 to 2.3 times the mass of ethyl 4-dihydroxyphenylacetic acid, followed by dissolution in deionized water, extraction with ethyl acetate, drying and concentration. S2. 2,4-Dimethoxymethoxyphenylacetic acid, 2-hydroxyethyl vinyl ether, p-toluenesulfonic acid and toluene are mixed in a mass ratio of 220~226:110~115:8:300, heated to 108~112℃, refluxed for 9~12h, cooled to room temperature, washed 3~5 times with saturated sodium bicarbonate, dried with anhydrous sodium sulfate, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain the methoxyvinyl ether copolymer; S3. Under an argon atmosphere, mix sodium hydride and tetrahydrofuran at a mass ratio of 3-4:50, place in an ice bath, and add dropwise a tetrahydrofuran solution containing polyoxymethylene dimethyl ether at a mass fraction of 8-12% (3-4 times the mass of sodium hydride) at a rate of 1-3 ml / min. Stir the reaction at 200-400 rpm for 20-30 min, then add dropwise a tetrahydrofuran solution containing allyl bromide at a mass fraction of 60-70% (8-10 times the mass of sodium hydride) at a rate of 1-3 ml / min. Raise the temperature to 60-62℃. The reaction was carried out for 5-6 hours, quenched with ice water, extracted with ethyl acetate, dried with anhydrous magnesium sulfate, and distilled under reduced pressure. Then, phthalimide peroxy acid, p-benzenesulfonic acid and toluene were added. The mass ratio of sodium hydride, phthalimide peroxy acid, p-benzenesulfonic acid and toluene was 1:8-9:0.22-0.25:6-7. The temperature was raised to 110-120℃ and refluxed for 10-12 hours. The mixture was cooled to room temperature, washed 3-5 times with saturated sodium bicarbonate, dried and distilled under reduced pressure to obtain epoxy polyoxymethylene dimethyl ether. S4. A composite impregnation solution is prepared by mixing nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer, and epoxy polymethoxydimethyl ether in a mass ratio of 0.5:1.2~1.5:0.2~0.24:0.3:0.05:0.03:0.3~0.6:0.2~0.3. S5. Adjust the pH of a 10-20% (w / w) methanol solution of hyperbranched polyamide-amine to 9-11 with sodium hydroxide, cool to 0-10℃, add epichlorohydrin at a rate of 1-3 ml / min under a nitrogen atmosphere, heat to 20-40 min, react for 4-6 h, quench with ice water and filter, rotary evaporate and vacuum dry to obtain epoxy polyamide-amine; S6. Under a nitrogen atmosphere, epoxy polyamide-amine and propylene glycol methyl ether acetate are mixed in a ratio of 1~1.1:2, heated to 115~125℃, stirred and dissolved, and then a mixture of dodecyl fluoroheptyl methacrylate (0.6~0.7 times the mass of epoxy polyamide-amine) is added dropwise at a rate of 1~3 ml / min. The mass ratio of dodecyl fluoroheptyl methacrylate, benzoyl peroxide and propylene glycol methyl ether acetate in the dodecyl fluoroheptyl methacrylate mixture is 22:1~2:40. After reacting for 1~2 h, the temperature is lowered to 70~72℃, and hyperbranched polyurethane (0.13~0.15 times the mass of epoxy polyamide-amine) and dibutyltin dilaurate (0.001~0.003 times the mass of epoxy polyamide-amine) are added. The reaction is continued for 20~30 min, and then the temperature is raised to 80~90℃ and held for 20~30 min to obtain fluorinated hyperbranched amide polyurethane. S7. Hydrogen-containing silicone oil, fluorinated hyperbranched amide polyurethane, and sorbitan monooleate are mixed at a mass ratio of 8~10:1~3:2. The mixture is stirred at 100~300 rpm for 10~20 min. Then, 0.01~0.02 times the mass of the hydrogen-containing silicone oil and Speier catalyst are added. The mixture is heated to 70~80℃ and reacted for 6~12 h. Finally, Tween-80, OP-10, and water are added. The mass ratio of hydrogen-containing silicone oil, Tween-80, OP-10, and water is 100:4~6:4~6:60. The mixture is sheared at 4000~5000 rpm for 20~30 min to obtain a waterproofing agent. S8. Impregnate the face paper in a composite impregnation solution at room temperature for 30-40 minutes, and then cure it under 800W ultraviolet light for 30-40 minutes to obtain a pre-cured face paper. Mix gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, retarder, glass fiber and water, stir into a slurry, and then add a foaming agent. After foaming, the porosity is 55-65%. The mass ratio of gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent, retarder, glass fiber and water is 35-45:3-8:3-5:2-4:1-3:1-3:3-5. Pour the mixture into a flat forming machine that presses the pre-cured face paper, and then attach another layer of pre-cured face paper to the surface. Hot press the mixture at a temperature of 180-200℃ and a pressure of 20-30MPa, and then dry, cut and saw the edges to obtain a high-strength moisture-proof gypsum board.

[0010] Preferably, the preparation method of ethyl 2,4-dihydroxyphenylacetate is as follows: ethyl 2,4-dimethoxyphenylacetate is cooled to -28 to -30°C, and a dichloromethane solution with a boron tribromide mass fraction of 14 to 16% is added dropwise at a rate of 1 to 3 ml / min, at a ratio of 20 to 30 times the mass of ethyl 2,4-dimethoxyphenylacetate. After the addition is complete, the temperature is raised to room temperature, and the reaction is allowed to proceed for 20 to 30 min. The temperature is then lowered to -2 to -5°C, quenched with saturated sodium bicarbonate solution, and the pH is adjusted to 6.8 to 7.2. After extraction with ethyl acetate, the mixture is separated by a chromatographic column of petroleum ether and ethyl acetate at a volume ratio of 4:1, followed by vacuum distillation to obtain ethyl 2,4-dihydroxyphenylacetate.

[0011] A preferred method for preparing phthalimide peroxyacid is as follows: phthalimide hexanoic acid and glacial acetic acid are mixed at a mass ratio of 2.1~2.2:2. Concentrated sulfuric acid (0.04~0.05 times the mass of phthalimide hexanoic acid) and 30% hydrogen peroxide (0.7~0.8 times the mass of phthalimide hexanoic acid) are added dropwise at a rate of 1~3 ml / min. The mixture is heated to 28~30℃ and reacted for 10~12 h. The pH is adjusted to 6~7 with ice water, and the precipitate is obtained. After filtration, the precipitate is recrystallized with ethyl acetate to obtain phthalimide peroxyacid.

[0012] Preferably, in step S5 above, the preparation method of hyperbranched polyamide-amine is as follows: ethylenediamine and methanol are mixed at a mass ratio of 3~4:50, placed in an ice bath, and methyl acrylate is added dropwise at a rate of 1~3 ml / min at a mass ratio of 3.5~4.5 times that of ethylenediamine. The mixture is reacted at room temperature for 24~28 h, distilled under reduced pressure, and then ethylenediamine at a mass ratio of 0.2~0.4 times that of methyl acrylate is added. The mixture is heated to 40~42℃ and reacted for 48~52 h. The mixture is then rotary evaporated and precipitated with diethyl ether, and dried under vacuum to obtain hyperbranched polyamide-amine.

[0013] Preferably, in step S5 above, the preparation method of hyperbranched polyurethane is as follows: diphenylmethylene diisocyanate and N,N-dimethylformamide are mixed at a mass ratio of 0.8~0.9:1, heated to 60~62℃, and a solution of N,N-dimethylformamide with a mass fraction of 40~50% diethanolamine is added dropwise at a rate of 1~3ml / min at 0.5~0.52 times the mass of diphenylmethylene diisocyanate. The reaction is maintained at this temperature for 2~3h, then heated to 80~82℃ and the reaction is continued for 2~3h. The mixture is quenched with methanol, cooled to room temperature, precipitated with deionized water, filtered, and dried at 60~70℃ to obtain hyperbranched polyurethane.

[0014] Preferably, in step S7 above, the method for preparing fluorinated silicone oil is as follows: under a nitrogen atmosphere, γ-trifluoropropylmethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, toluene, and the catalyst tetramethylammonium hydroxide are mixed in a mass ratio of 100:30:7:100:0.02~0.04, heated to 95~105℃, reacted for 5~7h, and then distilled under reduced pressure to obtain fluorinated silicone oil.

[0015] Compared with the prior art, the beneficial effects achieved by the present invention are: The high-strength moisture-proof gypsum board prepared by the present invention is made by impregnating the face paper in a composite impregnation liquid and then casting it with a gypsum core containing a waterproofing agent. The composite impregnation solution includes methoxy vinyl ether copolymer and epoxy polyoxymethylene dimethyl ether. The methoxy vinyl ether copolymer is prepared by reacting 2,4-dimethoxymethoxyphenylacetic acid with 2-hydroxyethyl vinyl ether. 2,4-dimethoxymethoxyphenylacetic acid is prepared by demethylating 2,4-dimethoxyphenylacetic acid to ethyl 2,4-dihydroxyphenylacetic acid, reacting it with chloromethyl methyl ether, and finally hydrolyzing it. The epoxy polyoxymethylene dimethyl ether is prepared by first end-capping polyoxymethylene dimethyl ether with allyl groups, and then reacting it with phthalimide peroxy acid. When combined with nano-silica and siloxane, it enhances the water resistance and bonding strength of the gypsum board face paper. At the same time, the methoxy groups and vinyl groups in the methoxy vinyl ether copolymer can participate in chemical reactions to form stable chemical bonds, while the epoxy groups in the epoxy polyoxymethylene dimethyl ether have excellent cross-linking ability and can react with calcium sulfate in the gypsum core and cellulose fibers in the face paper to form a three-dimensional network structure, thereby significantly improving the water resistance and mechanical properties of the gypsum board.

[0016] The waterproofing agent is prepared by reacting hydrogen-containing silicone oil with fluorinated hyperbranched amide polyurethane. The fluorinated hyperbranched amide polyurethane is prepared by reacting dodecafluoroheptyl methacrylate with epoxy polyamide-amine, followed by a reaction with hyperbranched polyurethane. The epoxy polyamide-amine is prepared by reacting hyperbranched polyamide-amine with epichlorohydrin. During the reaction between the hydrogen-containing silicone oil and the fluorinated hyperbranched amide polyurethane, the silicon-hydrogen bonds in the hydrogen-containing silicone oil undergo an addition reaction with the active groups in the fluorinated hyperbranched amide polyurethane, forming stable chemical bonds on the surface of the gypsum board. The formation of a dense hydrophobic layer effectively blocks moisture penetration, enhancing the bonding strength between the waterproofing agent and the gypsum core substrate. The introduction of fluorocarbon segments also improves the waterproofing agent's weather resistance and chemical corrosion resistance. During the curing process, the silicon-hydrogen bonds in the waterproofing agent undergo condensation reactions with the hydroxyl groups in the gypsum core and crosslink with the composite impregnation liquid, forming stable silicon-oxygen bonds and crosslinked structures. This further enhances the bonding strength between the gypsum core and the facing paper, thereby improving the moisture resistance and bonding strength of the gypsum board facing paper and providing additional mechanical support for the gypsum board. Detailed Implementation

[0017] The present invention will be specifically described below through embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those skilled in the art.

[0018] To more clearly illustrate the method provided by the present invention, the following embodiments are provided for detailed explanation. The test methods for various indicators of the high-strength moisture-proof gypsum boards prepared in the embodiments and comparative examples are as follows: Strength: The high-strength moisture-proof gypsum boards prepared in the examples and comparative examples were subjected to fracture load tests in accordance with GB / T9775.

[0019] Water resistance: The high-strength moisture-proof gypsum boards prepared in the examples and comparative examples were placed in an oven and dried at a constant temperature for 72 hours. They were then taken out and weighed (G1). They were then soaked in water for 1 day and 3 days respectively and taken out and weighed (G2). The water absorption rate of the gypsum board was calculated using the following formula: A = (G2 - G1) / G1 × 100%.

[0020] Adhesion: The adhesion grade of the high-strength moisture-proof gypsum prepared in the examples and comparative examples was tested for the face paper in accordance with GB / T9775.

[0021] Example 1 The preparation method of the high-strength moisture-proof gypsum board in this embodiment is as follows: S1. Ethyl 2,4-dimethoxyphenylacetate was cooled to -28°C, and a 14-16% (w / w) boron tribromide solution in dichloromethane was added dropwise at a rate of 1 ml / min, at a ratio of 20 times the mass of ethyl 2,4-dimethoxyphenylacetate. After the addition was complete, the temperature was raised to room temperature, and the reaction was allowed to proceed for 20 min. The temperature was then lowered to -2°C, quenched with saturated sodium bicarbonate solution, and the pH was adjusted to 6.8. The mixture was extracted with ethyl acetate, separated by a chromatographic column chromatography using petroleum ether and ethyl acetate at a volume ratio of 4:1, and distilled under reduced pressure to obtain ethyl 2,4-dihydroxyphenylacetate. Ethyl 2,4-dihydroxyphenylacetate and dichloromethane were mixed at a mass ratio of 1:15, cooled to 2°C, and 0.6-0.8 times the mass of sodium hydride (by weight of ethyl 2,4-dihydroxyphenylacetate) was added. At 200 rpm, 2, 1.9–2.1 times the mass of ethyl 4,4-dihydroxyphenylacetic acid was added to chloromethyl methyl ether, and the mixture was heated to room temperature and stirred for 10 h. After rotary evaporation, the mixture was extracted with dichloromethane and deionized water. Separation was performed by column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1. The mixture was then distilled under reduced pressure. Anhydrous ethanol (7 times the mass of ethyl 2,4-dihydroxyphenylacetic acid) and potassium hydroxide (0.2 times the mass of ethyl 2,4-dihydroxyphenylacetic acid) were added, and the mixture was heated to 32 °C and reacted for 4 h. After cooling to room temperature, acetic acid (2.1 times the mass of ethyl 2,4-dihydroxyphenylacetic acid) was added dropwise at a rate of 1 ml / min. The mixture was then distilled under reduced pressure, dissolved in deionized water, extracted with ethyl acetate, dried, and concentrated to obtain 2,4-dimethoxymethoxyphenylacetic acid. S2. 2,4-Dimethoxymethoxyphenylacetic acid, 2-hydroxyethyl vinyl ether, p-toluenesulfonic acid and toluene were mixed in a mass ratio of 220:110:8:300, heated to 108℃, refluxed for 9 h, cooled to room temperature, washed 3 times with saturated sodium bicarbonate, dried with anhydrous sodium sulfate, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain the methoxyvinyl ether copolymer; S3. Phthalimide hexanoic acid and glacial acetic acid were mixed at a mass ratio of 2.1:2. Concentrated sulfuric acid (0.04 times the mass of phthalimide hexanoic acid) and 30% hydrogen peroxide (0.7 times the mass of phthalimide hexanoic acid) were added dropwise at a rate of 1 ml / min. The mixture was heated to 28°C and reacted for 10 h. The pH was adjusted to 6 with ice water, and the precipitate was collected. After filtration, the precipitate was recrystallized with ethyl acetate to obtain phthalimide hexanoic acid. Under an argon atmosphere, sodium hydride and tetrahydrofuran were mixed at a mass ratio of 3:50 and placed in an ice bath. 8% tetrahydrofuran (a polyoxymethylene dimethyl ether) was added dropwise at a rate of 1 ml / min. The sodium hydride solution was stirred at 200 rpm for 20 min, and then a 60% tetrahydrofuran solution of allyl bromide was added dropwise at a rate of 1 ml / min. The temperature was raised to 60 °C and the reaction was carried out for 5 h. The reaction was quenched with ice water, extracted with ethyl acetate, dried with anhydrous magnesium sulfate, and distilled under reduced pressure. Phthalimide peroxy acid, p-benzylsulfonic acid and toluene were added. The mass ratio of sodium hydride, phthalimide peroxy acid, p-benzylsulfonic acid and toluene was 1:8:0.22:6. The temperature was raised to 110 °C and refluxed for 10 h. The reaction was cooled to room temperature, washed three times with saturated sodium bicarbonate, dried and distilled under reduced pressure to obtain epoxy polyoxymethylene dimethyl ether. S4. A composite impregnation solution is prepared by mixing nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer, and epoxy polymethoxydimethyl ether in a mass ratio of 0.5:1.2:0.2:0.3:0.05:0.03:0.3:0.2. S5. Ethylenediamine and methanol were mixed at a mass ratio of 3:50 and placed in an ice bath. Methyl acrylate (3.5 times the mass of ethylenediamine) was added dropwise at a rate of 1 ml / min. The mixture was reacted at room temperature for 24 h, followed by vacuum distillation. Then, ethylenediamine (0.2 times the mass of methyl acrylate) was added, and the mixture was heated to 40 °C and reacted for 48 h. The mixture was then rotary evaporated and precipitated with diethyl ether, and dried under vacuum to obtain hyperbranched polyamide-amine. A 10% (w / w) methanol solution of hyperbranched polyamide-amine was prepared by adjusting the pH to 9 with sodium hydroxide, cooling to 0 °C, and epichlorohydrin (2 times the mass of hyperbranched polyamide-amine) was added dropwise at a rate of 1 ml / min under a nitrogen atmosphere. The mixture was heated to 20 min, reacted for 4 h, quenched with ice water, filtered, rotary evaporated, and dried under vacuum to obtain epoxy polyamide-amine. S6. Diphenylmethylene diisocyanate and N,N-dimethylformamide were mixed at a mass ratio of 0.8:1, and the mixture was heated to 60°C. A solution of 40% diethanolamine in N,N-dimethylformamide, at a mass ratio of 0.5 times that of diphenylmethylene diisocyanate, was added dropwise at a rate of 1 ml / min. The mixture was kept at this temperature for 2 h, then heated to 80°C and reacted for another 2 h. The mixture was quenched with methanol, cooled to room temperature, precipitated with deionized water, filtered, and dried at 60°C to obtain hyperbranched polyurethane. Under a nitrogen atmosphere, epoxy polyamide-amine and propylene glycol methyl ether acetate were mixed at a ratio of 1:2 and the mixture was heated to 115°C. After stirring and dissolving, a mixture of dodecafluoroheptyl methacrylate (0.6 times the mass of epoxy polyamide-amine) was added dropwise at a rate of 1 ml / min. The mass ratio of dodecafluoroheptyl methacrylate, benzoyl peroxide, and propylene glycol methyl ether acetate in the dodecafluoroheptyl methacrylate mixture was 22:1:40. After reacting for 1-2 hours, the temperature was lowered to 70°C, and hyperbranched polyurethane (0.13 times the mass of epoxy polyamide-amine) and dibutyltin dilaurate (0.001 times the mass of epoxy polyamide-amine) were added. The reaction was continued for 20 minutes, and the temperature was raised to 80°C and held for 20 minutes to obtain fluorinated hyperbranched amide polyurethane. S7. Under a nitrogen atmosphere, γ-trifluoropropylmethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, toluene, and the catalyst tetramethylammonium hydroxide were mixed in a mass ratio of 100:30:7:100:0.02, heated to 95°C, reacted for 5 h, and then distilled under reduced pressure to obtain fluorinated silicone oil; hydrogen-containing silicone oil, fluorinated hyperbranched amide polyurethane, and sorbitan monooleate were mixed in a mass ratio of 8:1:2, stirred at 100 rpm for 10 min, and then Speier catalyst (0.012 times the mass of hydrogen-containing silicone oil) was added. The mixture was heated to 70°C and reacted for 6 h. Then Tween-80, OP-10, and water were added in a mass ratio of 100:4:4:60, and the mixture was sheared at 4000 rpm for 20 min to obtain a waterproofing agent; S8. The face paper is impregnated in a composite impregnation solution for 30 minutes at room temperature and then cured under 800W ultraviolet light for 30 minutes to obtain a pre-cured face paper. Gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, retarder, glass fiber and water are mixed and stirred into a slurry. A foaming agent is then added, and the porosity after foaming is 55%. The mass ratio of gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent sodium dodecyl sulfate, retarder sodium citrate, glass fiber and water is 35:3:3:2:1:1:3. The mixture is then poured into a flat forming machine that presses the pre-cured face paper. Another layer of pre-cured face paper is then attached to the surface. The mixture is then hot-pressed at a temperature of 180℃ and a pressure of 20MPa. After drying, cutting and sawing, a high-strength moisture-proof gypsum board is obtained.

[0022] Example 2 The preparation method of the high-strength moisture-proof gypsum board in this embodiment is as follows: S1. Ethyl 2,4-dimethoxyphenylacetate was cooled to -29°C, and a 15% boron tribromide solution in dichloromethane (25 times the mass of ethyl 2,4-dimethoxyphenylacetate) was added dropwise at a rate of 2 ml / min. After the addition was complete, the temperature was raised to room temperature, and the reaction was allowed to proceed for 25 min. The temperature was then lowered to -4°C, quenched with saturated sodium bicarbonate solution, and the pH was adjusted to 7.0. The mixture was extracted with ethyl acetate, separated by a chromatographic column of petroleum ether and ethyl acetate at a volume ratio of 4:1, and distilled under reduced pressure to obtain ethyl 2,4-dihydroxyphenylacetate. Ethyl 2,4-dihydroxyphenylacetate and dichloromethane were mixed at a mass ratio of 1.1:15, cooled to 3°C, and 0.7 times the mass of sodium hydride (3 times the mass of ethyl 2,4-dihydroxyphenylacetate) was added. At 300 rpm, 2, 2,4-Dimethoxyphenylacetic acid was prepared by adding chloromethyl methyl ether at twice the mass of ethyl 4,4-dihydroxyphenylacetic acid, heating to room temperature and stirring for 11 h, evaporating to dryness, extracting with dichloromethane and deionized water, separating by column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1, distilling under reduced pressure, adding anhydrous ethanol at eight times the mass of ethyl 2,4-dihydroxyphenylacetic acid and potassium hydroxide at 0.25 times the mass of ethyl 2,4-dihydroxyphenylacetic acid, heating to 34 °C and reacting for 5 h, cooling to room temperature, adding acetic acid at 2.2 times the mass of ethyl 2,4-dihydroxyphenylacetic acid at a rate of 2 ml / min, distilling under reduced pressure, dissolving in deionized water, extracting with ethyl acetate, drying and concentrating. S2. 2,4-Dimethoxymethoxyphenylacetic acid, 2-hydroxyethyl vinyl ether, p-toluenesulfonic acid and toluene were mixed in a mass ratio of 223:114:8:300, heated to 110℃, refluxed for 11 h, cooled to room temperature, washed 4 times with saturated sodium bicarbonate, dried with anhydrous sodium sulfate, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain the methoxyvinyl ether copolymer; S3. Phthalimide hexanoic acid and glacial acetic acid were mixed at a mass ratio of 2.15:2. Concentrated sulfuric acid (0.045 times the mass of phthalimide hexanoic acid) and 30% hydrogen peroxide (0.75 times the mass of phthalimide hexanoic acid) were added dropwise at a rate of 2 ml / min. The mixture was heated to 29°C and reacted for 11 h. The pH was adjusted to 6.5 with ice water, and the precipitate was collected. After filtration, the precipitate was recrystallized from ethyl acetate to obtain phthalimide hexanoic acid. Under an argon atmosphere, sodium hydride and tetrahydrofuran were mixed at a mass ratio of 3.5:50 and placed in an ice bath. 10% polyoxymethylene dimethyl ether (3.5 times the mass of sodium hydride) was added dropwise at a rate of 2 ml / min. A solution of hydrogen furan was stirred at 300 rpm for 25 min, and then a 65% tetrahydrofuran solution of allyl bromide was added dropwise at a rate of 2 ml / min at a mass ratio of 9 times that of sodium hydride. The mixture was heated to 61 °C and reacted for 5.5 h. The reaction was quenched with ice water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and distilled under reduced pressure. Phthalimide peroxy acid, p-benzylsulfonic acid, and toluene were then added. The mass ratio of sodium hydride, phthalimide peroxy acid, p-benzylsulfonic acid, and toluene was 1:8.5:0.24:6.5. The mixture was heated to 115 °C and refluxed for 11 h. After cooling to room temperature, the mixture was washed four times with saturated sodium bicarbonate, dried, and distilled under reduced pressure to obtain epoxy polyoxymethylene dimethyl ether. S4. A composite impregnation solution is prepared by mixing nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer, and epoxy polymethoxydimethyl ether in a mass ratio of 0.5:1.4:0.22:0.3:0.05:0.03:0.45:0.25. S5. Ethylenediamine and methanol were mixed at a mass ratio of 3.5:50 and placed in an ice bath. Methyl acrylate (4.0 times the mass of ethylenediamine) was added dropwise at a rate of 2 ml / min. The mixture was reacted at room temperature for 26 h, followed by vacuum distillation. Then, ethylenediamine (0.3 times the mass of methyl acrylate) was added, and the mixture was heated to 41 °C and reacted for 50 h. The mixture was rotary evaporated and precipitated with diethyl ether, and then dried under vacuum to obtain hyperbranched polyamide-amine. A 15% (w / w) methanol solution of hyperbranched polyamide-amine was prepared. The pH of the solution was adjusted to 10 with sodium hydroxide, and the temperature was lowered to 9 °C. Under a nitrogen atmosphere, epichlorohydrin (2 times the mass of hyperbranched polyamide-amine) was added dropwise at a rate of 2 ml / min. The mixture was heated to 25 min and reacted for 5 h. The mixture was quenched with ice water and filtered. The mixture was then rotary evaporated and dried under vacuum to obtain epoxy polyamide-amine. S6. Diphenylmethylene diisocyanate and N,N-dimethylformamide were mixed at a mass ratio of 0.85:1, heated to 61°C, and a solution of 45% diethanolamine in N,N-dimethylformamide (0.51 times the mass of diphenylmethylene diisocyanate) was added dropwise at a rate of 2 ml / min. The reaction was maintained at this temperature for 2.5 h, then heated to 81°C and reacted for another 2.5 h. The mixture was quenched with methanol, cooled to room temperature, precipitated with deionized water, filtered, and dried at 65°C to obtain hyperbranched polyurethane. Under a nitrogen atmosphere, epoxy polyamide-amine and propylene glycol methyl ether acetate were mixed at a mass ratio of 1.05:2 and heated to 12°C. At 0℃, after stirring and dissolving, a mixture of dodecafluoroheptyl methacrylate (0.65 times the mass of epoxy polyamide-amine) was added dropwise at a rate of 2 ml / min. The mass ratio of dodecafluoroheptyl methacrylate, benzoyl peroxide, and propylene glycol methyl ether acetate in the dodecafluoroheptyl methacrylate mixture was 22:1.5:40. After reacting for 1.5 h, the temperature was lowered to 71℃, and hyperbranched polyurethane (0.14 times the mass of epoxy polyamide-amine) and dibutyltin dilaurate (0.002 times the mass of epoxy polyamide-amine) were added. The reaction was continued for 25 min, and the temperature was raised to 85℃ and held for 25 min to obtain fluorinated hyperbranched amide polyurethane. S7. Under a nitrogen atmosphere, γ-trifluoropropylmethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, toluene, and the catalyst tetramethylammonium hydroxide were mixed in a mass ratio of 100:30:7:100:0.03, heated to 100°C, reacted for 6 hours, and then distilled under reduced pressure to obtain fluorinated silicone oil; the hydrogen-containing silicone oil, fluorinated hyperbranched amide polyurethane, and sorbitan monomethylsiloxane were then reacted. Oleate esters were mixed in a mass ratio of 9:2:2 and stirred at 200 rpm for 10-20 min. Speier catalyst with 0.015 times the mass of hydrogen-containing silicone oil was added, the temperature was raised to 75℃, and the reaction was carried out for 9 h. Tween-80, OP-10 and water were added, with a mass ratio of hydrogen-containing silicone oil, Tween-80, OP-10 and water of 100:5:5:60. The mixture was sheared at 4500 rpm for 25 min to obtain a waterproofing agent. S8. The face paper is impregnated in a composite impregnation solution for 35 minutes at room temperature and then cured under 800W ultraviolet light for 35 minutes to obtain a pre-cured face paper. Gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, retarder, glass fiber and water are mixed and stirred into a slurry. A foaming agent is then added, and the porosity after foaming is 60%. The mass ratio of gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent sodium dodecyl sulfate, retarder sodium citrate, glass fiber and water is 40:6:4:3:2:2:4. The mixture is then poured into a flat forming machine that presses the pre-cured face paper. Another layer of pre-cured face paper is then attached to the surface. The mixture is then hot-pressed at a temperature of 190℃ and a pressure of 25MPa. After drying, cutting and sawing, a high-strength moisture-proof gypsum board is obtained.

[0023] Example 3 The preparation method of the high-strength moisture-proof gypsum board in this embodiment is as follows: S1. Ethyl 2,4-dimethoxyphenylacetate was cooled to -30°C, and a 16% boron tribromide solution in dichloromethane (30 times the mass of ethyl 2,4-dimethoxyphenylacetate) was added dropwise at a rate of 3 ml / min. After the addition was complete, the temperature was raised to room temperature, and the reaction was allowed to proceed for 30 min. The temperature was then lowered to -5°C, quenched with saturated sodium bicarbonate solution, and the pH was adjusted to 7.2. The mixture was extracted with ethyl acetate, separated by a chromatographic column chromatography using petroleum ether and ethyl acetate at a volume ratio of 4:1, and distilled under reduced pressure to obtain ethyl 2,4-dihydroxyphenylacetate. Ethyl 2,4-dihydroxyphenylacetate and dichloromethane were mixed at a mass ratio of 1.2:15, cooled to 2-4°C, and 0.8 times the mass of sodium hydride (4 times the mass of ethyl 2,4-dihydroxyphenylacetate) was added. At 400 rpm, 2,4-dihydroxyphenylacetate was added... 2.1 times the mass of ethyl 4,4-dihydroxyphenylacetic acid was added to chloromethyl methyl ether, heated to room temperature and stirred for 12 h. After rotary evaporation, the mixture was extracted with dichloromethane and deionized water, separated by a chromatographic column of petroleum ether and ethyl acetate in a volume ratio of 4:1, and distilled under reduced pressure. Then, 9 times the mass of ethyl 2,4-dihydroxyphenylacetic acid in anhydrous ethanol and 0.3 times the mass of ethyl 2,4-dihydroxyphenylacetic acid in potassium hydroxide were added, heated to 35 °C and reacted for 6 h. After cooling to room temperature, 2.3 times the mass of ethyl 2,4-dihydroxyphenylacetic acid in acetic acid was added dropwise at a rate of 3 ml / min. The mixture was then distilled under reduced pressure, dissolved in deionized water, extracted with ethyl acetate, dried and concentrated to obtain 2,4-dimethoxymethoxyphenylacetic acid. S2. 2,4-Dimethoxymethoxyphenylacetic acid, 2-hydroxyethyl vinyl ether, p-toluenesulfonic acid and toluene were mixed in a mass ratio of 226:115:8:300, heated to 112°C, refluxed for 12 h, cooled to room temperature, washed 5 times with saturated sodium bicarbonate, dried with anhydrous sodium sulfate, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain the methoxyvinyl ether copolymer; S3. Phthalimide hexanoic acid and glacial acetic acid were mixed at a mass ratio of 2.2:2. Concentrated sulfuric acid (0.05 times the mass of phthalimide hexanoic acid) and 30% hydrogen peroxide (0.8 times the mass of phthalimide hexanoic acid) were added dropwise at a rate of 3 ml / min. The mixture was heated to 30°C and reacted for 12 h. The pH was adjusted to 7 with ice water, and the precipitate was collected. After filtration, the precipitate was recrystallized from ethyl acetate to obtain phthalimide hexanoic acid. Under an argon atmosphere, sodium hydride and tetrahydrofuran were mixed at a mass ratio of 4:50 and placed in an ice bath. 12% tetrahydrofuran (a polyoxymethylene dimethyl ether) was added dropwise at a rate of 3 ml / min. The sodium hydride solution was stirred at 400 rpm for 30 min, and then a 70% tetrahydrofuran solution of allyl bromide was added dropwise at a rate of 3 ml / min. The temperature was raised to 62 °C and the reaction was carried out for 6 h. The reaction was quenched with ice water, extracted with ethyl acetate, dried with anhydrous magnesium sulfate, and distilled under reduced pressure. Phthalimide peroxy acid, p-benzylsulfonic acid and toluene were added. The mass ratio of sodium hydride, phthalimide peroxy acid, p-benzylsulfonic acid and toluene was 1:9:0.25:7. The temperature was raised to 120 °C and refluxed for 12 h. The reaction was cooled to room temperature, washed 5 times with saturated sodium bicarbonate, dried and distilled under reduced pressure to obtain epoxy polyoxymethylene dimethyl ether. S4. A composite impregnation solution is prepared by mixing nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer, and epoxy polymethoxydimethyl ether in a mass ratio of 0.5:1.5:0.24:0.3:0.05:0.03:0.6:0.3. S5. Ethylenediamine and methanol were mixed at a mass ratio of 4:50 and placed in an ice bath. Methyl acrylate (4.5 times the mass of ethylenediamine) was added dropwise at a rate of 3 ml / min. The mixture was reacted at room temperature for 28 h, followed by vacuum distillation. Then, ethylenediamine (0.4 times the mass of methyl acrylate) was added, and the mixture was heated to 42 °C and reacted for 52 h. The mixture was rotary evaporated and precipitated with diethyl ether, and then dried under vacuum to obtain hyperbranched polyamide-amine. A 20% (w / w) methanol solution of hyperbranched polyamide-amine was prepared. The pH of the solution was adjusted to 11 with sodium hydroxide, and the temperature was lowered to 10 °C. Under a nitrogen atmosphere, epichlorohydrin (2 times the mass of hyperbranched polyamide-amine) was added dropwise at a rate of 3 ml / min. The mixture was heated to 40 min and reacted for 4 h. The mixture was quenched with ice water and filtered. The mixture was then rotary evaporated and dried under vacuum to obtain epoxy polyamide-amine. S6. Diphenylmethylene diisocyanate and N,N-dimethylformamide were mixed at a mass ratio of 0.9:1, heated to 62°C, and a solution of 40% diethanolamine in N,N-dimethylformamide (0.52 times the mass of diphenylmethylene diisocyanate) was added dropwise at a rate of 3 ml / min. The reaction was maintained at this temperature for 3 h, then heated to 82°C and reacted for another 2 h. The mixture was quenched with methanol, cooled to room temperature, precipitated with deionized water, filtered, and dried at 70°C to obtain hyperbranched polyurethane. Under a nitrogen atmosphere, epoxy polyamide-amine and propylene glycol methyl ether acetate were mixed at a mass ratio of 1.1:2 and heated to 12°C. At 5℃, after stirring and dissolving, a mixture of dodecafluoroheptyl methacrylate (0.7 times the mass of epoxy polyamide-amine) was added dropwise at a rate of 1 ml / min. The mass ratio of dodecafluoroheptyl methacrylate, benzoyl peroxide, and propylene glycol methyl ether acetate in the dodecafluoroheptyl methacrylate mixture was 22:2:40. After reacting for 2 h, the temperature was lowered to 72℃, and hyperbranched polyurethane (0.15 times the mass of epoxy polyamide-amine) and dibutyltin dilaurate (0.003 times the mass of epoxy polyamide-amine) were added. The reaction was continued for 30 min, and the temperature was raised to 90℃ and held for 30 min to obtain fluorinated hyperbranched amide polyurethane. S7. Under a nitrogen atmosphere, γ-trifluoropropylmethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, toluene, and the catalyst tetramethylammonium hydroxide were mixed in a mass ratio of 100:30:7:100:0.04, heated to 105°C, reacted for 7 h, and then distilled under reduced pressure to obtain fluorinated silicone oil; the hydrogen-containing silicone oil, fluorinated hyperbranched amide polyurethane, and sorbitan anhydride were then reacted. Monooleate was mixed in a mass ratio of 10:3:2 and stirred at 300 rpm for 20 min. Then, 0.02 times the mass of Speier catalyst containing hydrogen silicone oil was added, the mixture was heated to 80 °C, and reacted for 12 h. Tween-80, OP-10, and water were then added, with a mass ratio of hydrogen silicone oil, Tween-80, OP-10, and water of 100:6:6:60. The mixture was sheared at 5000 rpm for 30 min to obtain a waterproofing agent. S8. The face paper is impregnated in a composite impregnation solution for 40 minutes at room temperature and then cured under 800W ultraviolet light for 40 minutes to obtain a pre-cured face paper. Gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, retarder, glass fiber and water are mixed and stirred into a slurry. A foaming agent is then added, and the porosity after foaming is 65%. The mass ratio of gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent sodium dodecyl sulfate, retarder sodium citrate, glass fiber and water is 45:8:5:4:3:3:5. The mixture is then poured into a flat forming machine that presses the pre-cured face paper, and another layer of pre-cured face paper is attached to the surface. The mixture is then hot-pressed at a temperature of 200℃ and a pressure of 30MPa, and then dried, cut and sawed to obtain a high-strength moisture-proof gypsum board.

[0024] Comparative Example 1 The preparation method of Comparative Example 1 is the same as that of Example 2. The difference between this high-strength moisture-proof gypsum board and Example 2 is that the composite impregnation liquid only includes nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and methoxyvinyl ether copolymer.

[0025] Comparative Example 2 The preparation method of Comparative Example 2 is the same as that of Example 2. The difference between this high-strength moisture-proof gypsum board and Example 2 is that the composite impregnation liquid only includes nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, and epoxy polyoxymethylene dimethyl ether.

[0026] Comparative Example 3 The preparation method of Comparative Example 3 is the same as that of Example 2. The difference between this high-strength moisture-proof gypsum board and Example 2 is that the composite impregnation liquid only includes nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, and photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0027] Comparative Example 4 The preparation method of Comparative Example 4 is the same as that of Example 2. The difference between this high-strength moisture-proof gypsum board and Example 2 lies in the differences in S6. and S7., which are modified as follows: S6. Diphenylmethylene diisocyanate and N,N-dimethylformamide were mixed at a mass ratio of 0.85:1, heated to 61°C, and a 45% diethanolamine N,N-dimethylformamide solution was added dropwise at a rate of 2 ml / min at a mass ratio of 0.51 times that of diphenylmethylene diisocyanate. The reaction was maintained at this temperature for 2.5 h, then heated to 81°C and reacted for another 2.5 h. The mixture was quenched with methanol, cooled to room temperature, precipitated with deionized water, filtered, and dried at 65°C to obtain hyperbranched diisocyanate. In a nitrogen atmosphere, epoxy polyamide-amine and propylene glycol methyl ether acetate were mixed in a 1.05:2 ratio, heated to 120°C, and stirred until dissolved. Then, a mixture of dodecyl fluoroheptyl methacrylate (0.65 times the mass of epoxy polyamide-amine) was added dropwise at a rate of 2 ml / min. The mass ratio of dodecyl fluoroheptyl methacrylate, benzoyl peroxide, and propylene glycol methyl ether acetate in the dodecyl fluoroheptyl methacrylate mixture was 22:1.5:40. The reaction was carried out for 1.5 h to obtain fluorinated hyperbranched polyamide-amine. S7. Under a nitrogen atmosphere, γ-trifluoropropylmethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, toluene, and the catalyst tetramethylammonium hydroxide were mixed in a mass ratio of 100:30:7:100:0.03, heated to 100°C, reacted for 6 hours, and then distilled under reduced pressure to obtain fluorinated silicone oil; the hydrogen-containing silicone oil, fluorinated hyperbranched polyamide-amine, and sorbitan monosaccharide oil were then combined. The esters were mixed in a mass ratio of 9:2:2 and stirred at 200 rpm for 10-20 min. Then, 0.015 times the mass of the hydrogen-containing silicone oil and Speier catalyst were added. The mixture was heated to 75°C and reacted for 9 h. Tween-80, OP-10 and water were added in a mass ratio of 100:5:5:60. The mixture was sheared at 4500 rpm for 25 min to obtain the waterproofing agent.

[0028] Comparative Example 5 The preparation method of Comparative Example 5 is the same as that of Example 2. The difference between this high-strength moisture-proof gypsum board and Example 2 is that the waterproofing agent is prepared by reacting hydrogen-containing silicone oil with dodecafluoroheptyl methacrylate.

[0029] Comparative Example 6 The preparation method of Comparative Example 6 is the same as that of Example 2. The difference between this high-strength moisture-proof gypsum board and Example 2 is that the waterproofing agent is only hydrogen-containing silicone oil.

[0030] Example of effect Table 1 below presents the performance analysis results of the high-strength moisture-proof gypsum boards prepared using Examples 1 to 3 and Comparative Examples 1 to 6 of the present invention: Table 1

[0031] By comparing the experimental data of the examples and comparative examples in Table 1, it can be clearly found that the high-strength moisture-proof gypsum boards prepared using Examples 1, 2, and 3 have superior mechanical properties, moisture resistance, and adhesion.

[0032] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 reveals that the composite impregnation solution, combined with nano-silica and siloxane, enhances the water resistance and bonding strength of the gypsum board facing paper. Furthermore, the methoxy and vinyl groups in the methoxy vinyl ether copolymer can participate in chemical reactions to form stable chemical bonds, while the epoxy groups in the epoxy polyoxymethylene dimethyl ether possess excellent cross-linking capabilities, enabling them to react chemically with the calcium sulfate in the gypsum core and the cellulose fibers in the facing paper to form a three-dimensional network structure. This significantly improves the water resistance and mechanical properties of the gypsum board.

[0033] A comparison of the experimental data from Examples 1, 2, and 3 and Comparative Examples 4, 5, and 6 reveals that the hydrogen-silicon bonds in the hydrogen-containing silicone oil undergo an addition reaction with the active groups in the fluorinated hyperbranched amide polyurethane to form stable chemical bonds. This forms a dense hydrophobic layer on the gypsum board surface, effectively preventing moisture penetration. This not only enhances the bonding force between the waterproofing agent and the gypsum core substrate, but the introduction of fluorocarbon segments also improves the weather resistance and chemical corrosion resistance of the waterproofing agent. During the curing process, the hydrogen-silicon bonds in the waterproofing agent undergo a condensation reaction with the hydroxyl groups in the gypsum core and crosslink with the composite impregnation liquid to form stable silicon-oxygen bonds and crosslinked structures. This further enhances the bonding force between the gypsum core and the facing paper, thereby improving the moisture resistance and bonding strength of the gypsum board facing paper and providing additional mechanical support for the gypsum board.

[0034] Obviously, the above embodiments are merely examples to clearly illustrate the embodiments of the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively list all embodiments here. However, these obvious variations or modifications derived from the spirit of the present invention are still within the protection scope of the present invention.

Claims

1. A high-strength moisture-proof gypsum board, characterized in that, The raw material components include the following parts by weight: the paper is impregnated in a composite impregnation solution and then cast with a gypsum core containing a waterproofing agent; the composite impregnation solution includes nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer and epoxy polyoxymethylene dimethyl ether; the gypsum core includes gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent, retarder and glass fiber.

2. The high-strength moisture-proof gypsum board according to claim 1, characterized in that, The composite impregnation solution comprises a methoxyvinyl ether copolymer and an epoxy polyoxymethylene dimethyl ether; the methoxyvinyl ether copolymer is prepared by reacting 2,4-dimethoxymethoxyphenylacetic acid with 2-hydroxyethyl vinyl ether; the 2,4-dimethoxymethoxyphenylacetic acid is prepared by demethylating 2,4-dimethoxyphenylacetic acid to generate 2,4-dihydroxyphenylacetic acid, reacting it with chloromethyl methyl ether, and finally hydrolyzing it; the epoxy polyoxymethylene dimethyl ether is prepared by first end-capping polyoxymethylene dimethyl ether with allyl groups, and then reacting it with phthalimide peroxyacid.

3. The high-strength moisture-proof gypsum board according to claim 1, characterized in that, The waterproofing agent is prepared by reacting hydrogen-containing silicone oil with fluorinated hyperbranched amide polyurethane; the fluorinated hyperbranched amide polyurethane is prepared by reacting dodecafluoroheptyl methacrylate with epoxy polyamide-amine, and then reacting with hyperbranched polyurethane; the epoxy polyamide-amine is prepared by reacting hyperbranched polyamide-amine with epichlorohydrin.

4. The high-strength moisture-proof gypsum board according to claim 1, characterized in that, The foaming agent is sodium dodecyl sulfate; the retarder is sodium citrate.

5. The method for preparing a high-strength moisture-proof gypsum board according to claim 1, characterized in that, The specific steps include the following: S1. Mix ethyl 2,4-dihydroxyphenylacetate and dichloromethane at a mass ratio of 1-1.2:15, cool to 2-4°C, add 0.6-0.8 times the mass of ethyl 2,4-dihydroxyphenylacetate in sodium hydride, and add 1.9-2.1 times the mass of ethyl 2,4-dihydroxyphenylacetate in chloromethyl methyl ether at 200-400 rpm. Heat to room temperature and continue stirring for 10-12 hours. After rotary evaporation, extract with dichloromethane and deionized water, separate by column chromatography using petroleum ether and ethyl acetate at a volume ratio of 4:1, and distill under reduced pressure. Add 7-9 times the mass of ethyl 2,4-dihydroxyphenylacetate in anhydrous ethanol and 0.2-0.3 times the mass of ethyl 2,4-dihydroxyphenylacetate in potassium hydroxide, heat to 32-35°C, react for 4-6 hours, cool to room temperature, and add 2,4-dihydroxyphenylacetate dropwise at a rate of 1-3 ml / min. 2,4-Dimethoxymethoxyphenylacetic acid was prepared by vacuum distillation of 2.1 to 2.3 times the mass of ethyl 4-dihydroxyphenylacetic acid, followed by dissolution in deionized water, extraction with ethyl acetate, drying and concentration. S2. 2,4-Dimethoxymethoxyphenylacetic acid, 2-hydroxyethyl vinyl ether, p-toluenesulfonic acid and toluene are mixed in a mass ratio of 220~226:110~115:8:300, heated to 108~112℃, refluxed for 9~12h, cooled to room temperature, washed 3~5 times with saturated sodium bicarbonate, dried with anhydrous sodium sulfate, and then subjected to column chromatography with petroleum ether and ethyl acetate in a volume ratio of 4:1 to obtain the methoxyvinyl ether copolymer; S3. Under an argon atmosphere, mix sodium hydride and tetrahydrofuran at a mass ratio of 3-4:50, place in an ice bath, and add dropwise a tetrahydrofuran solution containing polyoxymethylene dimethyl ether at a mass fraction of 8-12% (3-4 times the mass of sodium hydride) at a rate of 1-3 ml / min. Stir the reaction at 200-400 rpm for 20-30 min, then add dropwise a tetrahydrofuran solution containing allyl bromide at a mass fraction of 60-70% (8-10 times the mass of sodium hydride) at a rate of 1-3 ml / min. Raise the temperature to 60-62℃. The reaction was carried out for 5-6 hours, quenched with ice water, extracted with ethyl acetate, dried with anhydrous magnesium sulfate, and distilled under reduced pressure. Then, phthalimide peroxy acid, p-benzenesulfonic acid and toluene were added. The mass ratio of sodium hydride, phthalimide peroxy acid, p-benzenesulfonic acid and toluene was 1:8-9:0.22-0.25:6-7. The temperature was raised to 110-120℃ and refluxed for 10-12 hours. The mixture was cooled to room temperature, washed 3-5 times with saturated sodium bicarbonate, dried and distilled under reduced pressure to obtain epoxy polyoxymethylene dimethyl ether. S4. A composite impregnation solution is prepared by mixing nano-silica, hydroxyl-terminated polydimethylsiloxane, vinyltrimethoxysilane, tetraethoxysilane, catalyst dibutyltin dichloride, photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propanone, methoxyvinyl ether copolymer, and epoxy polymethoxydimethyl ether in a mass ratio of 0.5:1.2~1.5:0.2~0.24:0.3:0.05:0.03:0.3~0.6:0.2~0.

3. S5. Adjust the pH of a 10-20% (w / w) methanol solution of hyperbranched polyamide-amine to 9-11 with sodium hydroxide, cool to 0-10℃, add epichlorohydrin at a rate of 1-3 ml / min under a nitrogen atmosphere, heat to 20-40 min, react for 4-6 h, quench with ice water and filter, rotary evaporate and vacuum dry to obtain epoxy polyamide-amine; S6. Under a nitrogen atmosphere, epoxy polyamide-amine and propylene glycol methyl ether acetate are mixed in a ratio of 1~1.1:2, heated to 115~125℃, stirred and dissolved, and then a mixture of dodecyl fluoroheptyl methacrylate (0.6~0.7 times the mass of epoxy polyamide-amine) is added dropwise at a rate of 1~3 ml / min. The mass ratio of dodecyl fluoroheptyl methacrylate, benzoyl peroxide and propylene glycol methyl ether acetate in the dodecyl fluoroheptyl methacrylate mixture is 22:1~2:

40. After reacting for 1~2 h, the temperature is lowered to 70~72℃, and hyperbranched polyurethane (0.13~0.15 times the mass of epoxy polyamide-amine) and dibutyltin dilaurate (0.001~0.003 times the mass of epoxy polyamide-amine) are added. The reaction is continued for 20~30 min, and then the temperature is raised to 80~90℃ and held for 20~30 min to obtain fluorinated hyperbranched amide polyurethane. S7. Hydrogen-containing silicone oil, fluorinated hyperbranched amide polyurethane, and sorbitan monooleate are mixed at a mass ratio of 8~10:1~3:

2. The mixture is stirred at 100~300 rpm for 10~20 min. Then, 0.01~0.02 times the mass of the hydrogen-containing silicone oil and Speier catalyst are added. The mixture is heated to 70~80℃ and reacted for 6~12 h. Finally, Tween-80, OP-10, and water are added. The mass ratio of hydrogen-containing silicone oil, Tween-80, OP-10, and water is 100:4~6:4~6:

60. The mixture is sheared at 4000~5000 rpm for 20~30 min to obtain a waterproofing agent. S8. Impregnate the face paper in a composite impregnation solution at room temperature for 30-40 minutes, and then cure it under 800W ultraviolet light for 30-40 minutes to obtain a pre-cured face paper. Mix gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, retarder, glass fiber and water, stir into a slurry, and then add a foaming agent. After foaming, the porosity is 55-65%. The mass ratio of gypsum powder, volcanic ash, cellulose nanocrystals, waterproofing agent, foaming agent, retarder, glass fiber and water is 35-45:3-8:3-5:2-4:1-3:1-3:3-5. Pour the mixture into a flat forming machine that presses the pre-cured face paper, and then attach another layer of pre-cured face paper to the surface. Hot press the mixture at a temperature of 180-200℃ and a pressure of 20-30MPa, and then dry, cut and saw the edges to obtain a high-strength moisture-proof gypsum board.

6. The method for preparing a high-strength moisture-proof gypsum board according to claim 5, characterized in that, In step S1 above, the preparation method of ethyl 2,4-dihydroxyphenylacetate is as follows: ethyl 2,4-dimethoxyphenylacetate is cooled to -28 to -30°C, and a dichloromethane solution with a boron tribromide mass fraction of 14 to 16% is added dropwise at a rate of 1 to 3 ml / min, at a ratio of 20 to 30 times the mass of ethyl 2,4-dimethoxyphenylacetate. After the addition is complete, the temperature is raised to room temperature, and the reaction is carried out for 20 to 30 min. The temperature is then lowered to -2 to -5°C, quenched with saturated sodium bicarbonate solution, and the pH is adjusted to 6.8 to 7.

2. After extraction with ethyl acetate, the mixture is separated by a chromatographic column of petroleum ether and ethyl acetate at a volume ratio of 4:1, and then distilled under reduced pressure to obtain ethyl 2,4-dihydroxyphenylacetate.

7. The method for preparing a high-strength moisture-proof gypsum board according to claim 5, characterized in that, In step S3 above, the preparation method of phthalimide peroxy acid is as follows: phthalimide hexanoic acid and glacial acetic acid are mixed at a mass ratio of 2.1~2.2:

2. Concentrated sulfuric acid (0.04~0.05 times the mass of phthalimide hexanoic acid) and 30% hydrogen peroxide (0.7~0.8 times the mass of phthalimide hexanoic acid) are added dropwise at a rate of 1~3 ml / min. The mixture is heated to 28~30℃ and reacted for 10~12 h. The pH is adjusted to 6~7 with ice water, and the precipitate is obtained. After filtration, it is recrystallized with ethyl acetate to obtain phthalimide peroxy acid.

8. The method for preparing a high-strength moisture-proof gypsum board according to claim 5, characterized in that, In step S5 above, the preparation method of hyperbranched polyamide-amine is as follows: ethylenediamine and methanol are mixed at a mass ratio of 3~4:50, placed in an ice bath, and methyl acrylate is added dropwise at a rate of 1~3 ml / min at a mass ratio of 3.5~4.5 times that of ethylenediamine. The mixture is reacted at room temperature for 24~28 h, distilled under reduced pressure, and then ethylenediamine at a mass ratio of 0.2~0.4 times that of methyl acrylate is added. The mixture is heated to 40~42℃ and reacted for 48~52 h. The mixture is then rotary evaporated and precipitated with diethyl ether, and dried under vacuum to obtain hyperbranched polyamide-amine.

9. The method for preparing a high-strength moisture-proof gypsum board according to claim 5, characterized in that, In step S6 above, the preparation method of hyperbranched polyurethane is as follows: diphenylmethylene diisocyanate and N,N-dimethylformamide are mixed at a mass ratio of 0.8~0.9:1, heated to 60~62℃, and a solution of N,N-dimethylformamide with a mass fraction of 40~50% diethanolamine is added dropwise at a rate of 1~3ml / min at 0.5~0.52 times the mass of diphenylmethylene diisocyanate. The reaction is maintained at this temperature for 2~3h, then heated to 80~82℃ and the reaction is continued for 2~3h. The mixture is quenched with methanol, cooled to room temperature, precipitated with deionized water, filtered, and dried at 60~70℃ to obtain hyperbranched polyurethane.

10. The method for preparing a high-strength moisture-proof gypsum board according to claim 5, characterized in that, In step S7 above, the preparation method of fluorinated silicone oil is as follows: under a nitrogen atmosphere, γ-trifluoropropylmethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, toluene and the catalyst tetramethylammonium hydroxide are mixed in a mass ratio of 100:30:7:100:0.02~0.04, heated to 95~105℃, reacted for 5~7h, and then distilled under reduced pressure to obtain fluorinated silicone oil.

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